201119969 六、發明說明： 【發明所屬之技術領域】 本發明有關具有覆蓋物、基板或上基板玻璃之光電模 組，以及特定玻璃在光電模組中作爲覆蓋物、基板或上基 板玻璃的有利用途。 【先前技術】 在光電裝置或在太陽能電池中，使用覆蓋物、基板及 上基板玻璃。覆蓋物玻璃具有保護該太陽能電池之敏感主 動組件不受外在環境影響（例如風、雨、雪、冰雹、灰塵 等）的任務。基板玻璃係用於沉積光電材料之薄層。上基 板玻璃在一體中執行基板玻璃與覆蓋物玻璃之任務。該等 玻璃必須符合的需求條件視個別模組槪念而定。因此’彼 等視所使用之半導體材料、視作爲基板、覆蓋物或上基板 玻璃等之功能而定。該覆蓋物與基板玻璃必須在個別相關 範園中顯示出高總透射率。此處，若可能的話，應避免在 表画上之反射損失及玻璃中之輻射吸收。 該等玻璃之透明度係與個別半導體匹配。如此，例如 以結晶矽（單晶或多晶）爲基底之模組在約400至1 2〇〇 nm 之波長範圍中具有最大敏感度。因此’在該範圍內之透射 率應最佳化。此外，由於該等玻璃係曝於連續改變的環境 應力下，故必須確保充足化學抗性。視該太陽能模組裝配 的場所而定，環境應力可能相當不同。因此所使用之玻璃 必須對於水、酸與鹼具有良好抗性。變化的溫度條件或結 -5- 201119969 霜亦造成特定需求。爲此，對於太陽能模組進行例如天候 條件的模擬改變（參見「濕熱測試」）。 基板與上基板玻璃另外必須承受塗層材料沉積作用中 的熱與化學應力。彼等必須承受例如導電透明層以及沉積 在其上之光電材料的沉積作用。此意指充分之耐熱性與對 於真空處理之抗性。 在先前技術中，由於鈉鈣玻璃之製造特別便宜，故廣 泛使用該等玻璃。然而，當用於製造光電模組或太陽能電 池時，彼#玻璃具有某些關鍵性缺點： - 鈉鈣玻璃之折射指數相當高，其nd爲約1.52。此 導致表面（特別是在玻璃空氣界面）之反射所造成的可用 輻射損失大； - 玻璃中之雜質導致可用輻射被該玻璃吸收。此處 ’鐵含量與鐵離子上之電荷特別重要。雖然該玻璃中之201119969 VI. Description of the Invention: [Technical Field] The present invention relates to a photovoltaic module having a cover, a substrate or an upper substrate glass, and an advantageous use of a specific glass as a cover, a substrate or an upper substrate glass in a photovoltaic module . [Prior Art] In a photovoltaic device or in a solar cell, a cover, a substrate, and an upper substrate glass are used. The cover glass has the task of protecting the sensitive active components of the solar cell from external environmental influences such as wind, rain, snow, hail, dust, and the like. The substrate glass is used to deposit a thin layer of photovoltaic material. The upper substrate glass performs the task of the substrate glass and the cover glass in one body. The requirements for such glass must meet the requirements of individual modules. Therefore, 'depending on the function of the semiconductor material used, whether it is a substrate, a cover or an upper substrate glass. The cover and substrate glass must exhibit high total transmittance in individual related fields. Here, if possible, the reflection loss on the surface and the absorption of radiation in the glass should be avoided. The transparency of these glasses is matched to individual semiconductors. Thus, for example, a module based on crystalline germanium (single crystal or polycrystalline) has maximum sensitivity in the wavelength range of about 400 to 12 〇〇 nm. Therefore, the transmittance within this range should be optimized. In addition, since these glass systems are exposed to continuously changing environmental stresses, sufficient chemical resistance must be ensured. Depending on where the solar module is assembled, the environmental stress can be quite different. Therefore, the glass used must have good resistance to water, acids and bases. Changing temperature conditions or knots -5 - 201119969 frost also creates specific needs. For this purpose, for the solar module, for example, a simulated change in weather conditions (see "Damp heat test"). The substrate and the upper substrate glass must additionally withstand the thermal and chemical stresses in the deposition of the coating material. They must withstand the deposition of, for example, a conductive transparent layer and the photovoltaic material deposited thereon. This means sufficient heat resistance and resistance to vacuum treatment. In the prior art, since soda lime glass is particularly inexpensive to manufacture, such glass is widely used. However, when used in the manufacture of photovoltaic modules or solar cells, the glass has certain key drawbacks: - The refractive index of soda lime glass is quite high, with an nd of about 1.52. This results in a large loss of available radiation due to reflections from the surface (especially at the glass-air interface); - impurities in the glass cause the available radiation to be absorbed by the glass. Here, the iron content and the charge on the iron ions are particularly important. Although in the glass
Fe3 +於約3 80 nm顯示出較弱及窄吸光作用，但同樣存在目 前所使用之所有太陽能玻璃中的Fe2 +離子導致在紅光至紅 外線波長範圍內之廣且強吸光作用。因此該等吸光帶造成 太陽光譜之可用輻射的顯著損失。爲此，使用特別純因而 昂貴之低鐵原料用作爲太陽能玻璃。 - 鈉鈣玻璃於以陽光照射（太陽能化）時具有透射 率損失。添加於玻璃中之多價離子（諸如鈽）特別易於產 生太陽能化。 根據EP 1 28 1 687 A1，使用具有低氧化鐵含量且額外 具備0.02 5至0 · 2重量％之氧化鈽的特純玻璃獲致高透射率 201119969 。此處’ FeO對Fe2〇3之特定比率及特別添加氧化铈相當重 要。 然而，維持特定Fe2 + /Fe3 +比率係相當難且昂貴的工作 。此外’特定含铈玻璃具有強烈太陽能化傾向。在極端實 例中’於強烈照射之後觀察到淡黃至淡棕色變色。 根據EP 1 29 1 3 3 0 A2，將具有低於0.020%之Fe203之 同樣具有低氧化鐵含量且添加0.0 0 6至2重量％氧化鋅的鈉 鈣玻璃用於太陽能電池。添加氧化鋅以對抗硫化鎳（NiS )的形成。最佳透明度需要氧化鐵對氧化鋅以及氧化铈之 特定比率》 如此又需要使用特定昂貴原料。較高氧化鈽含量亦會 具有反效果。 特別是，已發現高氧化鈽含量（例如參考EP 0 26 1 8 85 A1 )不利於強烈照射時之太陽能化。因此，具有至少 2重量％之氧化姉含量的此等玻璃被視爲不適用於太陽能 電池應用或光電應用。 於US 20〇7/0 1 44576 A1中提出使用鐵含量特別低之摻 雜銻的鈉鈣玻璃。特別是結合摻雜铈時，於強烈照射時此 處會出現因太陽能化所致之缺點。 【發明內容】 根據該背景，本發明目的係提出用作光電模組之覆蓋 物、基板或上基板玻璃的經改良玻璃及提出包含此種玻璃 之經改良光電模組。 201119969 在具有藉由添加受玻璃之鐵含量影響的特定最少含量 氟化物而含有氟化物之覆蓋物、基板或上基板玻璃的光電 模組中獲致本目的。此處，鐵含量對氟含量的重量比X = Fe/F爲至少0.001，較佳爲至少0.002，更佳爲至少0.005， 特佳爲至少〇.〇1。 以此種方式完全獲致本發明目的。已意外發現添加氟 化物分別導致該基底玻璃組成物的透射率改良；特別是， 可減少或補償該玻璃中存在氧化鐵的缺點。含氟化物玻璃 於未太陽能化狀態及太陽能化狀態之透射率高於具有其他 組成相同的習用無氟玻璃。經添加測量之氟離子明顯地造 成與氧化鐵之相互作用，其使得能消除或補償氧化鐵對於 透射表現的不利影響。 在本發明有利具體實例中，重量比X較佳係不大於0.6 ，更佳係不大於0.4，更佳係不大於0.2，特佳係不大於0.1 〇 特別是在受氧化鐵含量影響之氟化物精確計量添加中 ，該玻璃性質可超比例地提高且添加氟化物之缺點（例如 成本提高及因腐蝕性侵襲增加而導致之槽操作期限減少） 並未變明顯。基本上，可設定氟化物含量對鐵雜質含量之 最佳比率。若該比率低於此最佳値，則僅可獲致相當少之 正面透射率效果。若該比率高於此最佳値，則可觀察到該 透射率無進一步提高，且前文提及之負面效果佔優勢。 本發明之覆蓋物、基板或上基板玻璃較佳係具有0.02 至0.6之重量比率X。在該特定範圍內，於未太陽能化狀態 201119969 及太陽能化狀態二者的透射率均比其他組成相同之玻璃提 高。 除了前文提及之明確減少鐵雜質的負面效果之外，添 加氟化物形成進一步優點： - 氟化物降低玻璃之折射指數。此降低表面之反射 損失。如此，更大比例之可用輻射到達該太陽能電池。在 表I之實例中，觀察到之總透射率提高約1 /3係由此效果所 貢獻。 -•此外，已發現與習用鈉鈣玻璃相較之下，藉由添 加氟化物使熔性獲得改善。氟化物於此處係作爲熔融助劑 。以此種方式，該熔融溫度以及相關之能量成本可降低。 - 最後，藉由氟化物安定該玻璃。所觀察到之對於 環境影響（水、酸、鹼之侵襲）的意外高抗性可歸因於此 。此外，玻璃/聚合物膜界面明顯地受到正面影響。 將本發明含氟化物之玻璃用於太陽能電池或光電模組 首先可用以最大化效率。其次，藉由使用具有適當鐵含量 的較便宜之習用原料可能降低原料成本。特定鐵含量對於 玻璃熔體通常是有利的。因此，使用氟化物使得製造成本 更適宜及該等玻璃之良好透射性質最佳化。在節省成本的 同時’因添加氟化物使得熔融溫度降低因而造成較低能量 消耗，故而改善生態平衡。 在本發明第一具體實例中，該玻璃係已添加氟化物之 鈉鈣玻璃。 此可含有例如40至80重量。/。之Si02、0至50重量°/。之 201119969Fe3+ exhibits weaker and narrower absorption at about 380 nm, but there are also Fe2+ ions in all of the currently used solar glass that result in a broad and strong absorption in the red to infrared wavelength range. These light absorbing strips therefore cause a significant loss of available radiation in the solar spectrum. For this purpose, a particularly pure and therefore expensive low-iron raw material is used as the solar glass. - Soda lime glass has a loss of transmittance when exposed to sunlight (solarization). Multivalent ions (such as ruthenium) added to the glass are particularly prone to solarization. According to EP 1 28 1 687 A1, ultra-pure glass having a low iron oxide content and additionally having 0.02 5 to 0.2% by weight of cerium oxide is used to achieve high transmittance 201119969. Here, the specific ratio of FeO to Fe2〇3 and the addition of cerium oxide are particularly important. However, maintaining a specific Fe2 + /Fe3 + ratio is a rather difficult and expensive job. In addition, the specific bismuth-containing glass has a strong tendency to be solarized. In an extreme example, a pale yellow to light brown discoloration was observed after intense irradiation. According to EP 1 29 1 3 3 0 A2, soda lime glass having a low iron oxide content of less than 0.020% and having a low iron oxide content and adding 0.06 to 2% by weight of zinc oxide is used for the solar cell. Zinc oxide is added to combat the formation of nickel sulfide (NiS). The optimum transparency requires a specific ratio of iron oxide to zinc oxide and antimony oxide, which in turn requires the use of specific expensive materials. Higher yttrium oxide content can also have the opposite effect. In particular, high cerium oxide content (for example, reference EP 0 26 1 8 85 A1) has been found to be detrimental to solarization upon intense irradiation. Thus, such glasses having a cerium oxide content of at least 2% by weight are considered unsuitable for use in solar cell applications or photovoltaic applications. A soda-lime glass using a particularly low iron content is proposed in US Pat. No. 2,0,0,048,576 A1. In particular, when combined with erbium, there are disadvantages due to solarization during intense irradiation. SUMMARY OF THE INVENTION In light of this background, the present invention is directed to an improved glass for use as a cover for a photovoltaic module, a substrate or an upper substrate glass, and an improved photovoltaic module comprising such a glass. 201119969 This object was achieved in an optoelectronic module having a fluoride-containing cover, substrate or upper substrate glass by adding a specific minimum amount of fluoride which is affected by the iron content of the glass. Here, the weight ratio of iron content to fluorine content X = Fe/F is at least 0.001, preferably at least 0.002, more preferably at least 0.005, and particularly preferably at least 〇.〇1. The object of the invention is fully achieved in this way. It has been unexpectedly discovered that the addition of fluoride results in improved transmittance of the base glass composition, respectively; in particular, the disadvantage of the presence of iron oxide in the glass can be reduced or compensated. The transmittance of the fluoride-containing glass in the unsolarized state and the solarized state is higher than that of the conventional fluorine-free glass having the same composition. The addition of the measured fluoride ion clearly creates an interaction with the iron oxide which makes it possible to eliminate or compensate for the adverse effects of the iron oxide on the transmission performance. In an advantageous embodiment of the present invention, the weight ratio X is preferably not more than 0.6, more preferably not more than 0.4, more preferably not more than 0.2, and particularly preferably not more than 0.1, especially in the fluoride affected by the iron oxide content. In the precise metering, the properties of the glass can be increased in proportion and the disadvantages of adding fluoride (for example, increased cost and reduced tank operation time due to increased corrosive attack) are not apparent. Basically, the optimum ratio of fluoride content to iron impurity content can be set. If the ratio is lower than this optimum enthalpy, only a relatively small amount of positive transmittance effect can be obtained. If the ratio is higher than this optimum enthalpy, it can be observed that the transmittance is not further improved, and the negative effects mentioned above are dominant. The cover, substrate or upper substrate glass of the present invention preferably has a weight ratio X of from 0.02 to 0.6. Within this specific range, the transmittances in both the non-solarized state 201119969 and the solarized state are higher than those of the other compositions. In addition to the previously mentioned negative effects of reducing iron impurities, the addition of fluoride forms further advantages: - Fluoride reduces the refractive index of the glass. This reduces the reflection loss of the surface. As such, a greater proportion of the available radiation reaches the solar cell. In the example of Table I, an increase in the total transmittance observed of about 1/3 is contributed by this effect. -• In addition, it has been found that the melting is improved by the addition of fluoride compared to the conventional soda lime glass. Fluoride is used here as a melting aid. In this way, the melting temperature and associated energy costs can be reduced. - Finally, the glass is stabilized by fluoride. The unexpectedly high resistance observed for environmental influences (invasion of water, acid, and alkali) can be attributed to this. In addition, the glass/polymer film interface is clearly positively affected. The use of the fluoride-containing glass of the present invention in solar cells or photovoltaic modules can be used first to maximize efficiency. Second, the cost of raw materials can be reduced by using less expensive conventional materials with appropriate iron content. The specific iron content is generally advantageous for glass melts. Therefore, the use of fluoride makes the manufacturing cost more suitable and the good transmission properties of the glasses are optimized. While saving costs, the addition of fluoride reduces the melting temperature and thus lowers energy consumption, thereby improving the ecological balance. In a first embodiment of the invention, the glass is a soda lime glass to which fluoride has been added. This may contain, for example, 40 to 80 weights. /. SiO 2, 0 to 50 weight ° /. 201119969
Al2〇3、3至30重量％之R2〇、3至30重量％之R'O ’以及數量 爲〇至1〇重量％之其他成分，其中R係選自Li、Na及K所組 成之群組中的至少—種元素，且R'係選自Mg、Ca、Sr、 B a及Zn所組成之群組中的至少一種元素。 更佳者係使用含有5〇至76重量％之Si〇2、〇至5重量％ 之Al2〇3、6至25重量％之R2〇、6至25重量％之R'〇及數量爲 〇至1 〇重量％之其他成分且另外與氟化物摻合的鈉銘玻璃 〇 較佳者係添加至少〇. 1重量％，較佳係至少0.5重量％之 Al2〇3，主要係改良該玻璃之化學抗性以及其對於反玻化 之抗性。 此外，該含氟化物玻璃可爲例如已添加氟化物之硼矽 玻璃。 其可含有例如60至85重量％2Si〇2、1至10重量％之 Ah〇3、5至20重量％之B2〇3、2至10重量°/〇之尺2〇’及〇至1〇 重量％之其他成分，其中R係選自Li、N a及K所組成之群組 中的至少一種元素。 特別是，此可爲含有70至83重量％2Si02、1至8重量 %之Al2〇3、6至1 5重量％之B203、3至9重量％之R2〇 ’及〇 至1 0重量％之其他成分且已另外與氟化物摻合的玻璃。 此外，本發明之玻璃可爲例如含氟化物之鋁矽玻璃。 其通常可含有55至70重量％2Si〇2、10至25重量％之 A1203、0至5重量％2B2〇3、0至2重量％之R2〇、3至25重量 %之ΙΓΟ及數量爲0至1 〇重量％之其他成分’其中R係選自Li -10· 201119969 、Na及K所組成之群組中的至少一種元素，且R'係選自Mg 、C a、S r、B a及Ζ η所組成之群組中的至少一種元素。 此處，Β 2 Ο 3之添加較佳可爲至少〇 . 5重量％。此舉特別 在化學抗性及對於環境影響之抗性方面獲致進一步改善。 在本發明玻璃中，氧化鐵含量較佳可在0.005至0.25 重量％之範圍內。 在此範圍內，氧化鐵含量的負面影響大部分可由適當 之氟添加所補償。 此外，本發明之玻璃較佳可具有至少0.001重量％之氧 化姉含量，其較佳係侷限於不多於〇. 2 5重量％。以此種方 式，可改善本發明之玻璃的UV安定性而不會發生過度太 陽能化。 當然本發明之玻璃具有依光電模組之構造而定的適當 形狀。其可爲，例如平面玻璃或圓柱形或球面玻璃。亦可 能有其他形狀。 【實施方式】 實施例 表1顯示呈鈉鈣玻璃形式與硼矽玻璃形式之兩種不同 玻璃作爲對照實例1與對照實例2。彼等係慣用於光電模組 的玻璃。此外，本發明之實例分別爲實施例1之鈉鈣玻璃 及實施例2之硼矽玻璃。在實施例1中，已於其他成分中添 加0.3 g之氟，而在實施例2中，已於其他成分中添加0.5 g 之氟。應注意該表中之特徵並非以重量百分比計而是以絕 -11 - 201119969 對値計；轉換成重量百分比時會導致數値梢微改變。 比率X (即，鐵對氟之比率）係列於最後一行。亦列 出透射率，其顯示所有實例中該透射率均因添加氟化物而 提高。若使用具有較高氧化鐵含量之原料，則添加氟化物 比無添加氟化物之玻璃獲致更顯著改善。 從下圖1與2可更明顯看出添加氟化物對於透射率的影 響，該等圖式顯示對照實例1與實施例1以及對照實例2與 實施例2之透射率，各實例均於未太陽能化狀態及太陽能 化狀態。特別是在波長範圍爲400- 1 300 nm內，可觀察到 顯著改良之透射率。 鈉鈣玻璃 硼矽玻璃 玻璃成分（重量以g計） 對照實例1 實施例1 對照實例2 實施例2 Si02 71 71 81 81 Al2〇3 1 1 2 2 B2〇3 13 13 Li20 Na20 14 14 3 3 K20 1 1 MgO 4 4 CaO 10 10 Fe2〇3 0.012 0.012 0.008 0.008 Ce〇2 0.005 0.005 0.1 0.1 F 0.3 0.5 澄清劑 0.5 0.5 0.5 0.5 總計 100.517 100.817 100.608 101.108 廳率[%]丁 (400-1200)非太陽能化 91.22 91.52 92.96 93.05 透射率[%]丁 (400-1200)太陽能化 90.54 90.95 92.32 92.53 Fe X-—— F - 0.028 - 0.011 表1 201119969 【圖式簡單說明】 圖1顯示對照實例1與實施例1之透射率 圖2顯示對照實例2與實施例2之透射率 -13-Al2〇3, 3 to 30% by weight of R2〇, 3 to 30% by weight of R'O', and other components in an amount of from 〇 to 1% by weight, wherein R is selected from the group consisting of Li, Na and K At least one element in the group, and R' is selected from at least one element selected from the group consisting of Mg, Ca, Sr, B a and Zn. More preferably, it contains 5〇 to 76% by weight of Si〇2, 〇 to 5% by weight of Al2〇3, 6 to 25% by weight of R2〇, 6 to 25% by weight of R'〇, and the amount is 〇 to Preferably, at least 1% by weight, preferably at least 0.5% by weight, of Al 2 〇 3 is added to the other components of the 5% by weight of the other components, and the fluorochemical is modified. Resistance and its resistance to devitrification. Further, the fluoride-containing glass may be, for example, a boron bismuth glass to which fluoride has been added. It may contain, for example, 60 to 85% by weight of 2Si〇2, 1 to 10% by weight of Ah〇3, 5 to 20% by weight of B2〇3, 2 to 10% by weight/〇2〇' and 〇 to 1〇 % by weight of the other component, wherein R is at least one element selected from the group consisting of Li, Na and K. In particular, this may be from 70 to 83% by weight of 2SiO 2 , from 1 to 8% by weight of Al 2 〇 3, from 6 to 15 % by weight of B 203, from 3 to 9% by weight of R 2 〇 ' and from 〇 to 10% by weight. Glass of other ingredients that have been additionally blended with fluoride. Further, the glass of the present invention may be, for example, a fluoride-containing aluminum bismuth glass. It may generally contain 55 to 70% by weight of 2Si〇2, 10 to 25% by weight of A1203, 0 to 5% by weight of 2B2〇3, 0 to 2% by weight of R2〇, 3 to 25% by weight of ruthenium and the amount of 0. To 1% by weight of other components' wherein R is selected from at least one of the group consisting of Li -10·201119969, Na and K, and R' is selected from the group consisting of Mg, C a, S r, B a And at least one element of the group consisting of η η. Here, the addition of Β 2 Ο 3 may preferably be at least 〇 5% by weight. This has led to further improvements in chemical resistance and resistance to environmental influences. In the glass of the present invention, the iron oxide content is preferably in the range of 0.005 to 0.25 wt%. Within this range, the negative effects of the iron oxide content are mostly compensated by the appropriate fluorine addition. Further, the glass of the present invention preferably has a cerium oxide content of at least 0.001% by weight, which is preferably limited to not more than 0.25% by weight. In this manner, the UV stability of the glass of the present invention can be improved without excessive solarization. Of course, the glass of the present invention has an appropriate shape depending on the configuration of the photovoltaic module. It can be, for example, a flat glass or a cylindrical or spherical glass. There may be other shapes as well. [Embodiment] Examples Table 1 shows two different glasses in the form of soda lime glass and boron borosilicate glass as Comparative Example 1 and Comparative Example 2. They are used to glass for photovoltaic modules. Further, examples of the present invention are the soda lime glass of Example 1 and the borosilicate glass of Example 2, respectively. In Example 1, 0.3 g of fluorine was added to the other components, and in Example 2, 0.5 g of fluorine was added to the other components. It should be noted that the characteristics in this table are not in weight percent but in absolute terms -11 - 201119969; conversion to weight percent results in a slight change in the number of tips. The ratio X (ie, the ratio of iron to fluorine) is in the last row. Transmittance is also listed, which shows that the transmittance is increased by the addition of fluoride in all of the examples. If a raw material having a higher iron oxide content is used, the addition of fluoride is more significantly improved than the glass without the addition of fluoride. The effect of the addition of fluoride on the transmittance is more apparent from the following Figures 1 and 2, which show the transmittances of Comparative Example 1 and Example 1 and Comparative Example 2 and Example 2, each of which is in the absence of solar energy. State and solarization status. Particularly in the wavelength range of 400 - 1 300 nm, a significantly improved transmittance can be observed. Soda-lime glass borosilicate glass composition (weight in g) Comparative Example 1 Example 1 Comparative Example 2 Example 2 Si02 71 71 81 81 Al2〇3 1 1 2 2 B2〇3 13 13 Li20 Na20 14 14 3 3 K20 1 1 MgO 4 4 CaO 10 10 Fe2〇3 0.012 0.012 0.008 0.008 Ce〇2 0.005 0.005 0.1 0.1 F 0.3 0.5 Clarifier 0.5 0.5 0.5 0.5 Total 100.517 100.817 100.608 101.108 Office rate [%] D (400-1200) non-solar 91.22 91.52 92.96 93.05 Transmittance [%] D (400-1200) Solarization 90.54 90.95 92.32 92.53 Fe X-—— F - 0.028 - 0.011 Table 1 201119969 [Simplified Schematic] Figure 1 shows Comparative Example 1 and Example 1 Transmittance Figure 2 shows the transmittance-13- of Comparative Example 2 and Example 2.